Do coupling exciton and oscillation of electronhole pair exist in neutral and charged pidimeric quinquethiophenes?
(2007) In Journal of Chemical Physics 127(8). Abstract
 Optical physical properties of neutral and charged quinquethiophene monomer, and neutral and cationic pidimeric quinquethiophenes were investigated with density functional theory as well as the two dimensional (2D) site (transition density matrix) and three dimensional (3D) cube (transition density and charge difference density) representations, stimulated by the recent experimental report [T. Sakai , J. Am. Chem. Soc. 127, 8082 (2005)]. Transition density shows the orientation and strength of the transition dipole moment of neutral and charged quinquethiophene monomer, and charge difference density reveals the orientation and result of the charge transfer in neutral and charged quinquethiophene monomer. To study if coupling exciton and... (More)
 Optical physical properties of neutral and charged quinquethiophene monomer, and neutral and cationic pidimeric quinquethiophenes were investigated with density functional theory as well as the two dimensional (2D) site (transition density matrix) and three dimensional (3D) cube (transition density and charge difference density) representations, stimulated by the recent experimental report [T. Sakai , J. Am. Chem. Soc. 127, 8082 (2005)]. Transition density shows the orientation and strength of the transition dipole moment of neutral and charged quinquethiophene monomer, and charge difference density reveals the orientation and result of the charge transfer in neutral and charged quinquethiophene monomer. To study if coupling exciton and oscillation of electronhole pair exist in neutral and cationic pidimeric quinquethiophenes, the coupling constants J (coupling exciton of electronhole pair) and K (coupling oscillation of electronhole pair) were introduced to the exciton coordinate and momentum operators, respectively, and the 2D and 3D analysis methods were further developed by extending our previous theoretical methods [M. T. Sun, J. Chem. Phys. 124, 054903 (2006)]. With the new developed 2D and 3D analysis methods, we investigated the excited state properties of neutral and cationic pidimeric quinquethiophenes, especially on the coupling exciton and oscillation of electronhole pair between monomers. The 2D results show that there is neither coupling exciton (J=0) nor oscillation (K=0) of electronhole pair in neutral pidimeric quinquethiophenes. For some excited states of cationic pidimeric quinquethiophenes, there is no coupling exciton (J=0), but there is coupling oscillation (K not equal 0); while for some excited states, there are both coupling exciton and coupling oscillator simultaneously (J not equal 0 and K not equal 0). The strength of transition dipole moments of pidimeric quinquethiophenes were interpreted with 3D transition density, which reveals the orientations of their two subtransition dipole moments. The 3D charge transition density reveals the orientation and result of intermonomer and/or intramonomer charge transfer. The calculated results reveal that excited state properties of neutral pidimeric quinquethiophene are significantly different from those of the cationic pidimeric quinquethiophenes. (c) 2007 American Institute of Physics. (Less)
Please use this url to cite or link to this publication:
http://lup.lub.lu.se/record/687965
 author
 Sun, Mengtao; Liu, Liwei; Ding, Yong and Xu, Hongxing ^{LU}
 organization
 publishing date
 2007
 type
 Contribution to journal
 publication status
 published
 subject
 in
 Journal of Chemical Physics
 volume
 127
 issue
 8
 publisher
 American Institute of Physics
 external identifiers

 wos:000249156300063
 scopus:34548461270
 ISSN
 00219606
 DOI
 10.1063/1.2757175
 language
 English
 LU publication?
 yes
 id
 3eb2bb8565a6457c9ce36bd9926c0cbe (old id 687965)
 date added to LUP
 20080103 09:07:55
 date last changed
 20170723 03:56:44
@article{3eb2bb8565a6457c9ce36bd9926c0cbe, abstract = {Optical physical properties of neutral and charged quinquethiophene monomer, and neutral and cationic pidimeric quinquethiophenes were investigated with density functional theory as well as the two dimensional (2D) site (transition density matrix) and three dimensional (3D) cube (transition density and charge difference density) representations, stimulated by the recent experimental report [T. Sakai , J. Am. Chem. Soc. 127, 8082 (2005)]. Transition density shows the orientation and strength of the transition dipole moment of neutral and charged quinquethiophene monomer, and charge difference density reveals the orientation and result of the charge transfer in neutral and charged quinquethiophene monomer. To study if coupling exciton and oscillation of electronhole pair exist in neutral and cationic pidimeric quinquethiophenes, the coupling constants J (coupling exciton of electronhole pair) and K (coupling oscillation of electronhole pair) were introduced to the exciton coordinate and momentum operators, respectively, and the 2D and 3D analysis methods were further developed by extending our previous theoretical methods [M. T. Sun, J. Chem. Phys. 124, 054903 (2006)]. With the new developed 2D and 3D analysis methods, we investigated the excited state properties of neutral and cationic pidimeric quinquethiophenes, especially on the coupling exciton and oscillation of electronhole pair between monomers. The 2D results show that there is neither coupling exciton (J=0) nor oscillation (K=0) of electronhole pair in neutral pidimeric quinquethiophenes. For some excited states of cationic pidimeric quinquethiophenes, there is no coupling exciton (J=0), but there is coupling oscillation (K not equal 0); while for some excited states, there are both coupling exciton and coupling oscillator simultaneously (J not equal 0 and K not equal 0). The strength of transition dipole moments of pidimeric quinquethiophenes were interpreted with 3D transition density, which reveals the orientations of their two subtransition dipole moments. The 3D charge transition density reveals the orientation and result of intermonomer and/or intramonomer charge transfer. The calculated results reveal that excited state properties of neutral pidimeric quinquethiophene are significantly different from those of the cationic pidimeric quinquethiophenes. (c) 2007 American Institute of Physics.}, articleno = {084706}, author = {Sun, Mengtao and Liu, Liwei and Ding, Yong and Xu, Hongxing}, issn = {00219606}, language = {eng}, number = {8}, publisher = {American Institute of Physics}, series = {Journal of Chemical Physics}, title = {Do coupling exciton and oscillation of electronhole pair exist in neutral and charged pidimeric quinquethiophenes?}, url = {http://dx.doi.org/10.1063/1.2757175}, volume = {127}, year = {2007}, }